Autor según el artículo: Biosca M; Salto J; Magre M; Norrby P; Pamies O; Dieguez M

Departamento: Química Física i Inorgànica

Autor/es de la URV: Biosca Brull, Maria / Diéguez Fernández, Montserrat / Pamies Ollé, Oscar

Palabras clave: Palladium Nmr study N-ligands Molecular-orbital methods Modular ligands Mixed p,n-ligands Mixed p Kinetic resolution Force-field parameters Enantioselective allylation Dft calculations Cyclobutane backbone Basis-sets Asymmetric-synthesis Asymmetric allylic substitution Alkylation Ab-initio

Resumen: © 2019 American Chemical Society. A method for generation of Pd/phosphite-oxazoline catalysts containing an alkyl backbone chain has been successfully applied to Pd-catalyzed allylic substitution reactions. By carefully selecting the substituents at both the alkyl backbone chain and the oxazoline of the ligand, as well as the configuration of the biaryl phosphite group, high activities (TOF > 8000 mol substrate × (mol Pd × h)−1) and excellent enantioselectivities (ee's up to 99%) have been achieved for many hindered and unhindered substrates with a wide range of C-, O-, and N-nucleophiles (73 substitution products in total). Moreover, DFT and NMR studies of the key Pd-allyl complexes allowed us to better understand the origin of the excellent enantioselectivities observed experimentally. The useful application of the Pd/phosphite-oxazoline catalysts was demonstrated by the syntheses of many chiral carbobicycles, with multiples stereocenters, by simple sequential reactions involving Pd-allylic substitution and either 1,6-enyne cyclization or Pauson−Khand enyne cyclization.

Áreas temáticas: Química Materiais Interdisciplinar General chemistry Engenharias ii Ciências agrárias i Chemistry, physical Chemistry (miscellaneous) Chemistry (all) Catalysis Astronomia / física

Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 21555435

Direcció de correo del autor: maria.biosca@urv.cat montserrat.dieguez@urv.cat oscar.pamies@urv.cat

Identificador del autor: 0000-0002-9116-6318 0000-0002-8450-0656 0000-0002-2352-8508

Página final: 6048

Fecha de alta del registro: 2023-02-22

Volumen de revista: 9

Versión del articulo depositado: info:eu-repo/semantics/submittedVersion

Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/acscatal.9b01166

URL Documento de licencia: http://repositori.urv.cat/ca/proteccio-de-dades/

Referencia al articulo segun fuente origial: Acs Catalysis. 9 (7): 6033-6048

Referencia de l'ítem segons les normes APA: Biosca M; Salto J; Magre M; Norrby P; Pamies O; Dieguez M (2019). An improved class of phosphite-oxazoline ligands for Pd-catalyzed allylic substitution reactions. Acs Catalysis, 9(7), 6033-6048. DOI: 10.1021/acscatal.9b01166

DOI del artículo: 10.1021/acscatal.9b01166

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2019

Página inicial: 6033

Tipo de publicación: Journal Publications